Benzophenone hydrazones containing perfluoroalkyl,perfluoroalkoxy,and perfluoroalkylthio substituents

ABSTRACT

FLUORINATED BENZOPHENONE HYDRAZONES ARE BIOLOGICALLY ACTIVE AGAINST INSECTS AND SHOW ACTIVITTY IN INFLUENCING THE METABOLISM OF PLANTS.

United States Patent O 3,732,307 BENZOPHENONE HYDRAZONES CONTAINING PERFLUOROALKYL, PERFLUOROALKOXY, AND PERFLUOROALKYLTHIO SUBSTITUENTS William J. Middleton, Chadds Ford, Pa., assignor to E. I. du Pont de Nemonrs and Company, Wilmington, Del. No Drawing. Filed Sept. 24, 1970, Ser. No. 75,236 Int. Cl. C07c 109/16 U.S. Cl. 260-566 B 9 Claims ABSTRACT OF THE DISCLOSURE Fluorinated benzophenone hydrazones are biologically active against insects and show activity in influencing the metabolism of plants.

BACKGROUND OF THE INVENTION Field of the invention The present invention is in the field of biologically active chemicals and relates specifically to a novel class of benzophenone hydrazones which are insecticidally active and which show plant growth regulation and inhibition of plant senescence.

Prior art E. J. Forbes et a1., Tetrahydron 8, 67 (1960), describes the hydrazone:

which differs from the present invention in being a substituted hydrazone of an aldehyde.

1. R. DoAmaral et al., J. Med. Chem. 12, 21 (1969) and F. A. French, and Abstract of paper before Division of Medicinal Chemistry, Am. Chem. Soc., September 1969, describe the synthesis of antimalarial drugs of the structure:

.QQ-QX in which X and X are CF CF 0, halogen, hydrogen, alkyl, alkoxy, hydroxy, and dimethylamino. These differ in many respects from the compounds of the instant in- 3,732,307 Patented May 8, 1973 "ice ' wherein X and Y may occupy the ortho, meta or para vention in being hydrochloride salts, in having the hydra- I This invention relates to a class of biologically useful hydrazones of benzophenones that are substituted with at least one flourine-containing substituent. They have the formula NHz positions and X is selected from the group consisting of perfluoroalkyl,

perfluoroalkoxy, and perfluoroalkylthio groups containing up to four carbon atoms, and

Y is selected from the group consisting of hydrogen, chlorine, bromine, fluorine, alkyl, alkoxy, alkylthio, perfluoroalkyl, perfiuoroalkoxy, and perfluoroalkylthio groups containing up to four carbon atoms.

The novel hydrazones may exist as the synand antiisomers;

NHa H2N X I l Y X I l Y Q- Q (II) (III) SPECIFIC EMBODIMENTS OF THE INVENTION The tollowing examples, in which all parts or percentages are by weight unless otherwise stated, are intended as illustrative and non-limitative embodiments of the invention. The syntheses of benzophenones not previously reported in the literature are included in the appropriate examples.

EXAMPLE 1 v 4-trifluoromethylbenzophenone hydrazone, mixture of isomers X=CF and Y=H NH2NH2 I C H CO- CFa CuHs-C- C a-F A solution of 250 g. (1.0 mole) of 4-trifluoromethylbenzophenone and ml. of anhydrous hydrazine in 2 liters of ethanol was refluxed for 65 hours and then cooled and poured into l0 liters of water. The solid precipitate that formed was collected on a filter, washed with water, and then dried in vacuum over P 0 to constant weight. There was obtained 256.3 g. (97%) of a mixture of the two isomeric forms of 4-trifluoromethylbenzophenone as a white crystalline powder, M.P. 50105 C. The F n.m.r. spectrum of this mixture in CCl F indicated that the two isomers are present in the ratio of 45:55.

Analysis.Calcd. for C H F N (percent): C, 63.63; H, 4.20; F, 21.57; N, 10.60. Found (percent): C, 63.68; H, 4.25; F, 21.71; N, 10.39.

EXAMPLE 2 4-trifluoromethylbenzophenone hydrazone, high melting isomer X=CF and Y=H A 20-g; sample of a 45:55 mixture of the two isomeric hydrazones from Example 1 was dissolved in alcohol and fractionally precipitated by the addition, of water. Five H, 4.20; F, 21.57; N, 10.60. Found (percent): C, 64.10;

H, 4.29; F, 21.41; N, 10.89.

7 EXAMPLE 3 I -4-trifluoromethylbenzophenone hydrazone, low melting isomer X=CF and Y=H A 20-g. sample of a 45:55 mixture of the two isomeric hydrazones from'Example 1 was dissolved in alcohol and fractionally precipitated bythe addition of water. Five grams of: the more soluble (last to precipitate) fraction was fractionally recrystallized from pentane to give 3.34

g. of the more soluble isomer as large colorless crystals:

M.P. 59-60' C.; UV (ethanol) k 287111;]. (6 13,200) and 223 m (6 11,600); F N.M.R. (CCl F) 6 63.7 p.p.m. (quintet, J=0.6 Hz.) from CClgF- Analysis.-Calcd. for C H F N (percent): C, 63.63; H, 4.20; F, 21.57; N, 10.60. Found (percent): 'C, 63.50; H, 4.02; F, 21.69'N, 10.82.

EXAMPLE 4 3-trifluoromethylbenzophenone hydrazone X=CF and Y=H FgC ' 'A solution of 54.5 g. (0.3 mole) of phenylmagnesium bromide in 100 ml. of ether was added dropwise to a solution of 43 g. (0.25 mole) of 3-trifiuoromethylbenzonitrile in 100 ml. of ether. Concentrated hydrochloric. acid (100 ml.) was added dropwise and the solid that formed was collected'on a filter and washed with a little water and then ether. There was obtained 68 g. of a light-yellow granular solid. A suspension of 57 g. of this solid in 200 ml. of 10% HCl was heated to boiling for 5 minutes. The -oil that resulted solidified upon cooling and was collected on a filter. Recrystallization from pentane gave 3-trifluoromethylbenzophenone as colorless plates, M.P. 47- 48 C.

A solution of 25g. (0.1 mole) of 3-trifluoromethylbenzophenone and g. of anhydrous hydrazine in 200 .ml. of ethanol was refluxed for 40 hours, and then poured into 800 ml. of water and extracted with CCI F. The extract was washed with water, dried with MgSO and distilled to give 13.97 g. of 3-trifluoromethylbenzophenone I hydrazone as a colorless oil: B.P. 133-136 C. (1.0 mm);

EXAMPLE 5 4trifluoromethoxybenzophenone hydrazone X=CF O and Y=H cum-Qt: CuHr g r 3 --N--MgBr H01 0F=0- c I H2O A solution of 21.7 g. (0.12 mole) of phenylmagnesium bromide in 40 ml. of ether was added dropwise to a stirred solution of 18.7 g. (0.1 mole) of 4-trifluoromethoxybenzonitrile in 100 ml. of ether. The mixture was stirred for 1 hour at C., and then 100 m1. of 100% of hydrochloric acid was added dropwise wtih stirring. Theprecipitate that 'formed was collected ona filter, washed with ether,

and then stirred with 100 ml. of boiling 10% hydrochloric acid for 5 minutes. The oilthat formed solidified upon cooling. The solid was collected'on a filter and washed with water.

p The ether layer of the original reaction mixture was separated and evaporated to dryness to give a solid residue.

. The solids .were combined and recrystallized two times .withdecolorizing charcoal from pentane to give 18.70 .g. (70%) of r4-trifluoromethoxybenzophenone as colorless 332 my. (6 152) and 252 In,u. (e.17,500).

Analysis.-Calcd. for C H F O (percent): C, 63.16;

H, 3.41; F, 21.41.'Found (percent) :'-C, 63.44; H, 3.42; p

. a NHzNHy y Y F A solution of 10.64 g. (0.04 mole) of 4-trifluoromethoxybenzophenone and 4 ml. of anhydrous hydrazine in 80 ml. of alcohol was refluxed for 60 hours and then cooled and poured into 200 mLof water. The organic layer was extracted with CCl F, and the extract was washed with water, dried with MgSO and distilled to give 6.95 g. of 4-trifluorornethoxybenzophenone hydrazone as a colorless liquid: B.P. 141-142" C. (1.4 mm.);, 11 1.5584; U.V. (ethanol) a 275 me (e 12,000); F N.M.R. (CCI F) 6 58.3 p.p.m. (In).

Ahalysis-Calcd. for C I-I F N 0 (percent): C, 60.00; H, 3.96; -F, 20.34; N, 10.00. Found (percent): C, 60.12; H 4.02; F, 20.38; N, 9.76. v

EXAMPLE 6 i v f 4- (trifluoromethylthio)benzophenone hydrazone X=CF S and Y=H A solution of 21.7. g. (0.12 mole) of phenylmagnesium bromide in 40 ml. of ether was added dropwise to a stirred solution of 20.3 g. (0.1 mole) of 4-(trifluoromethylthio)benzonitrile in 100 'ml. of ether. The mixture was stirred for 1 hour. at 25 C., and then 100 ml. of 10% hydrochloric acid was added dropwise with stirring. The precipitate that formed was collected on a filter, washed with ether, and then stirred with 100 ml. of boiling 10% hydrochloric acid for 5 minutes. The oil that formed solidified upon cooling. The solid was collected on a filter and washed with water.

The ether layer of the original reaction mixture was evaporated to dryness to give a solid residue. The solids were combined and recrystallized two times with decolorizing charcoal from pentane to give 20.45 g. (72%) of 4-(trifluoromethylthio)benzophenone as colorless crystals; M.P. 6869 C.; IR (K-Br) 6.03 L; UV (ethanol) A 336 m (6 174); 256 m (6 16,800); F n.m.r. (CCl F) 6 42.5 p.p.m. (s).

Analysis.Calcd. for C H F OS (percent): C, 59.57; H, 3.21; F, 20.19; '8, 11.36. Found (percent): C, 59.69; H, 3.22; F, 20.22; S, 11.95.

synand antiisomers A solution of 11.3 g. (0.04 mole) of 4-(trifluoro methylthio)benzophenone and 4 ml. of anhydrous hydrazine in 80 ml. of ethanol was refluxed for 60 hours and then cooled and poured into 200 ml. of water. The organic layer was extracted with CCl F, and the extract was dried witH'MgSO; and distilled to give 6.45 g. of 4-(trifluoromethylthio)benzophenone hydragzone as a colorless liquid: B,P, 155-160" C. (1.0 mm-.); 11 1.5988; UV (ethanol) M 290 m (e- 13,600); 9F n.m.r. (CCl F) 6 42.8 p.p.m.'(s, 33%) and 43.2'p.p.m. (s, 67%).

Analysis.-Calcd. for C H F N S (percent); C, 56.74; H, 3.75; F, 19.24; N, 9.46; S, 10.82. Found '(percent): C, 56.74; H, 3.69; F, 19.62; N, 9.22; S, 10.88.

EXAMPLE 7 Preparation of 4,4'-bis(trifluoromethyDbenzdphenone hydrazone X and =CF H'Br" A solution of 10 g. of '4',4-bis(trifluorom'ethyl)benzo phenone,5.8g. of anhydrous hydrazine and 25 m1. of absolute alcohols was defluxed for 7 hours and cooled in ice after standing overnight at room temperature. White crystalline 4,4 131'5 (trifluoromethyDbenzophenone hydrazone was filtered from the solution and washed with cold ethanol, and air-dried: 6.2 g. M.P. 87.5 -C.;" H n.m.r. (acetone-d /CCl F) 2.47 7' (multi- "plet, SI-l) 7.25 "r '-'(b r oad multiplet, 2H). F n.m.r. (acet0ne-d /CCl F internal standard) '5 62.6 p.p.m. (singlet, 3F) 6 62.9 p.p.m. (singlet, 3F

EXAMPLE 8 Preparation of 4-perfluoroisopropylbenzophenone hydrazone (mixture of synand anti-isomers) 1. wormerQ-m 2. 10% HBr (CFmCFQ A solution of 32.5 g. (0.1 mole) of p-perfluoroisopropylbromobenzene in 50 ml. of ether was added dropwise to 0.1 mole of n-butyllithium in 63 ml. of n-hexane and 150 m1. of ether at 0-10 C. to obtain p-perfluoroisopropylphenyllithium which remained in solution. A solution of 10.3 g. (0.1 mole) of benzonitrile in 50 ml. of ether was added at 010 C. and the mixture stirred for 1 hour, poured into of 10% H'Br solution which has been cooled in ice. A sample of 4-perfiuoroisopropylbenzophenone was filtered from solution (18.7 g. after drying) and washed with Water and ether. The organic layer was washed with water, dried with MgSO and distilled to give 1.5 g. of 4-perfluoroisopropylbenzo- "phenone as a colorless liquid which crystallized on standing to a white solid. Total yield of 4-perfluoropropylbenzophenone, 20.2 g. (58%); B.P. -114 C. (0.6 mm.');"M.-P. 46-48" C.; F n.m.r. (CCl F) 6 76.1 p.p.m. (doublet, J-=7 Hz., 6F) 6 183 p.pm. (septet, J =7 Hz.

"to CF 1F).

. benzophenonehydrazoneas a colorless viscous liquid:

B.P. 137 C. (0.8 mm.); F n.r n'.r.- (CCl F); 6 76.2 p.p.m. (two overlapping doublets,J isomer A=13.0 Hz., Iisomer B=15.5 Hz., 6F) 8 183 p.p.m. (multiplet, 1F). AnaZysis.-Calcd. for C H N F (percent): C, 52.77; H, 3.02; N, 7.69; F, 36.52. Found (percent) C, 52.72; H, 3.41; N, 6. 85;" F, 3'5,98.

EXAMPLE 9 15 4-methoxy- -trifluoromethylbenzophenone hydrazone X=CF and Y' =OCH Cmoqx arm-Gon Nm 10% c1 To 37.4 g. (0.2 mole) p-bromoanisole in 400 ml. ether was added dropwise a solution of 0.2 mole n-butyllithium in 100 ml. n-hexane at 0-10". To this solution was added 34.2 g. (0.2 mole) p-trifluoromethylbenzonitrile in 100 35 8 methylbenzophenone, which was recrystallizedfrom ethanol-water to give'28.1 g. (58%) of white crystals, M.Pl 1191'21. 'l I s Analysis.Calcd. for C H -O -F (percent)':'C, 64.28; H, 3.96; F, 20.34. Found (percent): C,.'64.49; H, 3.96; F; 19.91. F

. no... omoQ-b-Q-cm +NHiNHz W L OGH.

l A solution of 10 g. 4,-methoxy-4-trifiuoromethyl benzophenone, 6g. anhydrous hydrazine andml. ethanol was refluxed 7 hr. On coolingin ice a solid formed'and was filtered off, washed with water and dried to give 6.5 g. solid which was recrystallized from ethanol/water to give one isomer of 4-methoxy-4'-trifluoromethyl benzophenone hydrazone: l V L-P. 97-99; F (ether, CCl F std.) 6 63.3 p.p.m. (s). H

Analysis.-Calcd. for C H N OF (percent): C, 61.22; H, 4.46; N, 9.52; F, 19.36. Found (percent): C, 60.96; H, 4.58; N, 9.23; F, 19.59.

The hydrazones listed in Table I can be prepared by the procedure described in Example 7, except that the ptrifluoromethylbenzonitrile in that examples is replaced by the indicated benzonitriles, and the resulting benzophenones are treated with hydrazine.

TABLE I Example number Beuzonitrile ml. ether at 0=10. The solution was stirred 15 minutes Prpducthydrazone NH:I

The .hydrazones listed in Table H can be prepared by the procedure described in Example 7, except that the p- .trifluoromethylbromobenzene in that example, is replaced by the indicated bromobenzenes, and the resulting benzophenones are treated with hydrazine.

or3 crz)3 s Br l TABLE 1r Example 7 v Y Y number Bromobenzene Product hydrazone 15 r i v w t NH:

0M0 Foe-QM 16 v I NH,

( z)s r I 17 NHT orns- Br 7 a,

18 I l I IlH:

a( 1)a l The hydrazones listed in Table III can be prepared by Compositions the procedure described inExample7, except that .the p-trifluoromethylbromobenzeneIis replaced by the indicated bromobenzenes, and: =ithe v.p-trifiuoromethylbenzonitrile is replaced by the'indicated benzonitriles. The resulting benzophenones are-treated withihydrazine. The benzonitrile in Example 19 can be prepared from m-(perfiuorobutyl)aniline by means of the Sandmeyer Reaction (the aniline is first treated with NaNO in cold dilute HCl, and then with KCN in the presence of cuprous salts). The brornobenzene in Example 22 can be prepared by the reaction of p-bromophenyl-magne'sium bromide with perfluorobutylsulfenyl chloride'in ether. The sulfenyl' chloride can be prepared by the reaction of chlorine with perfluorobutyl disulfide in an autoclave at 150 C.

TABLE III Example number Bromobenzene s Benzonitrile Product hydrazone 19 N NH:

CF3(CF7)3 Br l 11] (C F3)3CF3 omc r m-Q 3(C 2)a C 20 i NH,

CH;(CH:) Br CF3O- ON 111 7,, 0 F3 NH:

(ll CH3(CH:) 0- CN. F- I Br 1 1;: 313

CN NH I 2 CF3 III I of similar type..'Sui'table surface active agents are set out, for example, in Detergents and Emulsifiers Annual-- 11968v by John W. McCutcheon, Inc. Other surface active agents not listed by McCutcheon but stillefliective dispersants by virtue of protective colloid action include I -methyl cellulose, polyvinyl alcohol, hydroxyethylcellulose, and alkyl-substituted polyvinyl pyrrolidones.

Suitable surface active agents for use in compositions include polyethylene glycol esters" with fatty and rosin acids, polyethylene glycol ethers with alkyl phenols or with long-chain aliphatic alcohols, polyethylene glycol dialkyl esters of alkali metal sulfosuccinates, fatty acid esters of amine, alkali and alkaline earth isethionates and taurates, amine, alkali and alkaline earth salts of lignin sulfonic acids, methylated or hydroxyethylated cellulose,, polyvinyl alcohols, alkyl substituted polyvinyl pyrrolidone, amine, alkali and alkaline earth salts of polymerized alkylnaphthalene sulfonic acids, and long-chain quaternary ammonium compounds. Anionic and nonionic sur'- I face active agents are preferred.

Among preferred wetting agents are sodium alkyl naphthalene sulfonates, sodium dioctylsulfosuccinate, sodium dodecylbenzene sulfonate, ethylene, oxide conden sates with alkylated phenols such as octylfnonyl and dodecyl phenol, sodium lauryl sulfate, and trimethylnonyl are sodium, calcium and magnesium lignin sulfonates, low viscosity methyl cellulose, low-viscosity polyvinyl alcohol, alkylated polyvinyl pyrrolidone, polymerized alkyl naphthalene sulfonates, sodium N-oleyl or N-lauryl isethionates sodium N-meth'yl-N-palmitoyl taurate and -dodecyl phenol polyethylene glycol esters; Among preferred emulsifying agents are ethylene oxide adducts of lauric, oleic, palmitic or stearic acid esters surfactants. 7

Compositions containing the new compounds of this invention will contain, in addition to surface active agents, solid or liquid diluents to produce wettable powders, dusts or emulsifiable liquids as desired.

(A) Wettable powders Wettable-powders are eempesitions-whiclr-usuallyazonso that adhesion to dew-covered foliage is enhanced.

polyethylene glycols. Among preferrd"dispe'fsing "agents" 4' undersidenearwartimepewaas"wili"fisually"abstain tain inert solid diluents in addition to surfactants. These inert diluents may-sewe-several purposes-*I-hey-can-acb; "as grinding aids to prevent mill smear and screen blinding, they can aid rapid dispersion of the mix when placed in water, they can absorb liquid or low melting solid active material toproduce a free-"flowing solid product, they can prevent agglomeration into lumps upon prolonged hot storage and they can permit preparation of compositions ,witha controlled amount of active ingredient so that proper dosage is easily measured by the consumer- Suitable diluents may be either inorganic or organicin origin. These include the natural clays, diatomaceous earth, synthetic mineral fillers derived from silica or silicates, insoluble salts produced by' precipitation in flulfy 'form such as tricalcium phosphate or calcium carbonate,

synthetic. silicas synthetic calcium and. magnesium sili.- cates and diatomaceous silica.

Wettable powders will normally contain both a wetter and a dispersant. Most preferred for dry wettable powders are those anionic and nonionic surfactantswhich exist in solid form. Occasionally a liquid, nonionic surfactant, xnormally considered an emulsifying agent can be used ,'to produce both wetting and dispersion.

- Wetting and dispersing agents in wettable powders con- -taining the compounds of this invention, when taken together, will comprise from about 0.5 weightpercent to 12 5.0 Weightpercent of the total composition. The active component-wilhbe present at a concentration of-from about 15% .to and diluentmakes up the balance to-%. Where needed a corrosion inhibitor orfoaming inhibitor may be added at ratesof 0.1% to, 1.0% with a corresponding reduction in diluent.

(B) Dusts Dust compositions are those intended forappucation in dry form with suitable dusting equipment. Since wind drift is undesirable when applying dusts, the most suitable dust diluents are those which are dense and rapid settling. These include kaolinites, tales, pyrophyllites,.. ground phosphate rock, sericite, and groundtobacco'stems. However, dusts are usually most easily prepared by diluting an existing high-strength composition or wettable powder with a dense diluent so that the final dust will frequently contain a fraction. of li'g'ht, absorptive diluent'aswell'as the more desirable dense filler. U

1 A- wettingt agent may be desirable in dust formulations I Emulsifiable. liquids are formulatedby combining the compounds of this invention with a suitable emulsifier and an} organic'liquid with low watersolubility. Theactive component may be completely dissolved in the organic liquid or it may be a finely ground suspension in a nonsolvent liquid. Suitable organic liquids include alkylated naphthalenes, xylene, high molecular weight ketones,..sucl1. asisophorones, -dibutyl .01; diamylwketnn esters such as amyl acetate andnormal or iso parafiins. Mostpreferred. emulsifiers are blends ofno'ilsolublesulfo nates and nonionic polyoxyethylene glycol esters or ethers of fatty acids of alkylated phenols.

The-active component in emulsifiable concentrates will be' present at from 10 weightpercent to about 40 weight percent. Combined emulsifiers will be present at from 3 weight percent to about 10 weight'percent andthe balance will be an organic carrier liquid or solvent.

While conventional applications of sprayable formulations have usually been made in a dilute form (for example at a rate of about 200 liters per'li'ectare' ormore), the compounds of this invention can also-be applied at higher concentrations in the typical ultra-low-volume" or low-volume applications from aircraft or ground sprayers. For this purpose wettable powders can be dispersed in small amounts of aqueous or non-aqueous carrier. The suspension for emulsifiable concentrates can be used directly or with minor dilution. Special compositions, particularly suitable for ULV applications are solu-' phatic hydrocarbons (halogenated and non-halogenated) 3 EXAMPLE A Wettable powders: Percent p-(Trifluoromethyl)benzophenone, hydrazone--- 31 Sodium alkylnaphthalenesulfonate 4 Sodium ligninsulfonate 4 Kaolin clay 55 Hydrated silica 6 The ingredients are combined, mixed, micropulverized and then blended. The resulting powder wets and disperses readily in water and is suitable for application in normal spray equipment. Any of the other hydrazones may be substituted for the active ingredient here to give useful wettable powder.

EXAMPLE B Percent p-(Trifiuoromethyl)benzophenone, hydrazone 30.5 Sodium alkylnaphthalenesulfonate 2 Methyl cellulose, low viscosity 2 Calcium ligninsulfonate 2 Diatomaceous silica 63.5

The ingredients are combined, mixed, micropulverized and then blended.

EXAMPLE C Dust: Percent p-(Trifluoromethyl)benzophenone, hydrazone-" 5 Attapulgite clay 5 Talc 90 The materials are combined and stirred until a clear solution is formed.

The hydrazones of the invention also possess insecticidal properties, and can be used to protect crops from insects. For example compounds of Examples 3, 5, 6 and 9 gave 100% kill of army worms when applied as a 0.2% aqueous spray to crop plants. A spray was formulated in each instance by dissolving the compound in 10 ml. acetone and diluting with water cointaining Duponol (Du Pont trademark) as a wetting agent. Red kidney bean plants were sprayed about 8 days after planting (primary leaves). When dry, a 2 inch leaf disc was cut from the leaf and put in a petri dish with 10 Southern Army worm larvae which were 12 days from hatch and about inch long. At a spray concentration of 0.2% solution, a 100% kill was observed.

The following example illustrates improvement of wheat yield through the application of the product of Example 1:

EXAMPLE E Spring wheat variety Selkirk was grown in controlled environment rooms under continuous 2500 footcandle light at 70 F.; the growth medium was expanded vermiculite which had been previously washed with dilute acid to remove alkaline buffering capacity.

All plants were watered twice daily with Hoaglands nutrient solution. Test plants were treated at 30, 37, 44, 51, 58 or 65 days after planting; one one set was treated at all of the above times. Each 1% quart can (containing two plants( received 60 ml. of a 236 p.p.m. water suspension of 4-trifiuoromethylbenzophenone hydrazone (45% low melting isomer and 55% high melting isomer) poured around the plant base eight hours after the regular watering with nutrient solution; the plants were watered again with nutrient solution after 16 hours. Control plants were treated exactly as test plants except that 60 ml. distilled 14 water was substituted for the 4-trifiuoromethylbenzophenone hydrazone suspension.

At 30 days, the seedhead was just emerging from the boot (leaf sheath from which the seedhead, or cluster, emerges); at 65 days, the plants had started to senesce visibly.

All plants were harvested days after planting. The mature and immature seedheads were counted and weighed. The experimental data are collected in Table IV.

TABLE IV [The effect of p-trifiuoromethylbenzophenone hydrazone on the number and weight of Wheat (var. Selkirk) seedheads expressed as percent of control] Number of seedheads Weight of seedheads Treatment Imma- Immatime (days) Mature ture Total Mature ture Total 128 158 135 118 140 120 122 215 147 120 173 125 120 227 149 108 167 114 115 184 133 106 147 110 123 210 146 126 140 127 65 106 185 127 120 140 122 All of above. 130 127 128 100 131 It is concluded from the above experimental data that p-tri-fluoromethylbenzophenone hydrazone aifects at least the two plant development stages of flowering and fruit development. Both the number of seedheads and weight per seedhead were increased.

EXAMPLE -F Selected Concord grape vines in a commercial vineyard were treated with one or two applications of 4-trifluoromethylbenzophenone, hydrazone. Plants treated once were treated only at anthesis; plants treated twice were treated at aathesis and again 16 days later. The chemical was applied to runoff as a suspension in water containing 0.1% polyethylene sorbitan monolaurate. At harvest the following results (average of four replications) were obtained:

2. The compound of claim 1 wherein X is trifluoromethyl and Y is hydrogen.

3. The compound of claim 2 which is 4-trifiuoromethylbenzophenone hydrazone.

4. The compound of claim 2 which is 3-trifluoromethylbenzophenone hydrazone.

5. The compound of claim 1 wherein X is trifluoromethoxy and Y is hydrogen.

6. The compound of claim 1 wherein X is trifluoromethylthio and Y is hydrogen.

1 s 7. The compound of claim 1 wherein each of X and Y OTHER REFERENCES are mfluommethyl' v Beilsteins Handbuch der Organischem Chemie, vo '1 bog} (1:11: ggglngzlitgygfogianlfl 1 wherern le perfluoro p. 9 (1968) I. v m zi gig figgf gi f 1 wherein X 5 BERNARD HELEN, Primary Examiner I 1 4 G. A. SCHWARTZ,'Assistant Examiner References Cited UNITED STATES'PATENTS US. Cl. X.R.

2,710,862 6/1955 Schroeder 260566 B X 10 424--327; 71-121 PQ-wao UNITED STATES PATENT @FFE 5/ A 69) CERTIFIQATE m mnmmien Patent No. 3 Z 3 ;3 7 Date& y 973 I Inventofls) William J o Middleton It is certified that error appem'e in the nnove-ifientifiec'i patent and that said Letters Patent are hereby correctefi ae ehcwn Kaelow:

001.. 3, line 12, "011 should be c5 001. A, line 19, "100%" should be 10% 001. 5, line 30 in the right hand formula, H-NH should be N-NH --'3 line 73, add after mole 2 Col, 8, line 33, "examples" should be example Col. 9, Example 17, the formula under the column headed "Bromobenzene", "CH S' should be (EH 3 Example 21, Table lnunder "Benzonitrile" 0H (cH }0" should be CH3(CH2)3O C01. 11, line 28, add a comma. after Mates" Signed and sealed this 19th day of February 1974.

Attest: A A .1

EDWARD M.FLETCHER,JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents UNITED-STATES PATENT" OFFICE CERTIFICATE OF CORRECTION Patent No. 3 732307 Dated; May 8. 1972 Inventr(3) J. Middleton It is certified that error appears in the above-identified patent and. that said Letters Patent are hereby corrected as shown below:

olumn 2 line 15 should be changed to:

H Y H Y -Q 0 0 (II) I (III) Signed and sealed this 15th day of October 1974,

(SEAL) Attest:

MCCOY M. GIBSON JR. 7 c. MARSHALL DANN Attesting Officer 7 Commissioner of Patents 

